Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures.

Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure.

It is highly desirable but technically challenging to precisely control the spatial composition and internal structure of crystalline nanocomposite materials, especially in a one-pot synthetic route. Herein, we demonstrate a versatile pathway to tune the spatial distribution of guest species within a host inorganic crystal via an incorporation strategy. Specifically, well-defined block copolymer nanoparticles, poly(methacrylic acid)x-block-poly(styrene-alt-N-phenylmaleimide)y [PMAAx-P(St-alt-NMI)y], are synthesized by polymerization-induced self-assembly. Such anionic nanoparticles can supra-assemble onto the surface of larger cationic nanoparticles via an electrostatic interaction, forming colloidal nanocomposite particles (CNPs). Remarkably, such CNPs can be incorporated into calcite single crystals in a spatially controlled manner: the depth of CNPs incorporation into calcite is tunable. Systematic investigation indicates that this interesting phenomenon is governed by the colloidal stability of CNPs, which in turn is dictated by the PMAAx-P(St-alt-NMI)y adsorption density and calcium ion concentration. This study opens up a general and efficient route for the preparation of a wide range of crystalline nanocomposite materials with a controlled internal composition and structure.

Synergistic Effect of Hydroxyl and Carboxyl Groups on Promoting Nanoparticle Occlusion within Calcite.

Direct occlusion of guest nanoparticles into host crystals enables the straightforward preparation for various of nanocomposite materials with emerging properties. Therefore, it is highly desirable to elucidate the 'design rules' that govern efficient nanoparticle occlusion. Herein, a series of sterically-stabilized nanoparticles are rationally prepared, where the surface stabilizer chains of such nanoparticles are composed of either poly(methacrylic acid), or poly(glycerol monomethacrylate), or poly((2-hydroxy-3-(methacryloyloxy)propyl)serine). Systematic investigation reveals that hydroxyl groups and carboxyl groups play a synergistic role in driving nanoparticle incorporation into calcite crystals, where the hydroxyl groups enhance colloidal stability of the nanoparticles and the carboxyl groups provide binding sites for efficient occlusion. The generality of these findings is further validated by extending it to polymer-stabilized gold nanoparticles. This study demonstrates that precision synthesis of polymer stabilizers comprising of synergistic functional groups can significantly promote nanoparticle occlusion, thus enabling the efficient construction of organic-inorganic hybrid materials via nanoparticle occlusion strategy.

Controlled Deformation of Soft Nanogel Particles Generates Artificial Biominerals with Ordered Internal Structure.

Biominerals can exhibit exceptional mechanical properties owing to their hierarchically-ordered organic/inorganic nanocomposite structure. However, synthetic routes to oriented artificial biominerals of comparable complexity remain a formidable technical challenge. Herein we design a series of soft, deformable nanogels that are employed as particulate additives to prepare nanogel@calcite nanocomposite crystals. Remarkably, such nanogels undergo a significant morphological change-from spherical to pseudo-hemispherical-depending on their degree of cross-linking. This deformation occurs normal to the growth direction of the (104) face of the calcite and the underlying occlusion mechanism is revealed by in situ atomic force microscopy studies. This model system provides new mechanistic insights regarding the formation of oriented structures during biomineralization and offers new avenues for the design of synthetic nanocomposites comprising aligned anisotropic nanoparticles.

Optomechanical squeezing with pulse modulation.

Quantum control technology provides an increasingly useful toolbox for quantum information tasks. In this Letter, by introducing a pulsed coupling to a standard optomechanical system, we show that stronger squeezing can be obtained with pulse modulation due to the reduction of the heating coefficient. Also, the general squeezed states, such as the squeezed vacuum, squeezed coherent, and squeezed cat states, can be obtained with their squeezing level exceeding 3 dB. Moreover, our scheme is robust to cavity decay, thermal temperature, and classical noise, which is friendly to experiments. The present work can extend the application of quantum engineering technology in optomechanical systems.

Metal-Organic Frameworks@Calcite Composite Crystals.

The direct incorporation of guest crystals into another type of host crystals during the formation of the latter is technically challenging due to the large difference in surface energy for different crystalline components. Nevertheless, we herein demonstrate that metal-organic frameworks (MOFs, UiO-66-NH2 as a model guest crystal) after postsynthetic modification with poly(methacrylic acid) can be efficiently incorporated into calcite single crystals, forming a unique composite structure where the MOF crystals are uniformly distributed throughout the whole calcite host crystals. Remarkably, such MOF@calcite composite crystals exhibit superior performance in fluoride removal compared with the MOF or calcite alone. Moreover, this incorporation strategy is general as it can be extended to other guest particles. In principle, this study opens up a versatile avenue for the rational design and preparation of a wide range of hybrid functional materials with controllable compositions and enhanced physicochemical properties.

Distribution, sources and risk assessment of PAHs in soil from the water level fluctuation zone of Xiangxi Bay, Three Gorges Reservoir.

Information on PAH distribution in the water level fluctuation zone (WLFZ) of Three Gorges Reservoir is limited. In this study, we investigated PAH distribution and sources and assessed PAH risks, over one annual water level fluctuation cycle (June 2017-June 2018) at four elevations spanning the WLFZ (145 m, 155 m, 165 m and 175 m) at seven locations in the water level fluctuation zone along Xiangxi River. The mean total PAH concentration in June 2018 (953 ng g-1) was significantly higher than in June 2017 (494 ng g-1), and the horizontal and vertical distributions of PAHs changed significantly. The changes in distribution patterns provided evidence for the cause of increased PAH levels, which were attributed to construction of the Xiangxi River Bridge. Thus, this study of PAH dynamics in the WLFZ soils of Xiangxi Bay also provided valuable information on the impact of bridge construction on WLFZ soils. The change in PAH levels among stations implicated sediment disturbance resulting from bridge construction as the major contributor to the increased PAH levels. Source characterization, based on the ratios of certain PAHs, indicates that PAHs are mainly from the combustion of petroleum fuels, biomass and coal. These ratios indicated that the proportion of PAHs from fuel combustion increased from 2017 to 2018, implicating the heavy equipment used during bridge construction as another source of the increased PAH levels. The incremental lifetime cancer risk (ILCR) model was used to assess the health risk of the PAHs and the range among all age groups (10-5-10-4) indicates a potential health risk. The mean effects range-median quotient (M-ERM-Q) was used to assess the ecological risk of PAHs and the range (0.1-0.5) indicates low to medium risk. The increase in PAH levels from 2017 to 2018 increased the risk to public health and the environment. The results of this investigation provide a reference for ecological restoration of the WLFZ and support development of effective policies for environmental and public health. Further, the results provide information on the impact of bridge construction on WLFZ soils and identify research needed to more fully understand PAH dynamics in WLFZ soils.

Improving few-photon optomechanical effects with coherent feedback.

Few-photon effects such as photon blockade and tunneling have potential applications in modern quantum technology. To enhance the few-photon effects in an optomechanical system, we introduce a coherent feedback loop to cavity mode theoretically. By studying the second-order correlation function, we show that the photon blockade effect can be improved with feedback. Under appropriate parameters, the photon blockade effect exists even when cavity decay rate is larger than the single-photon optomechanical coupling coefficient, which may reduce the difficulty of realizing single-photon source in experiments. Through further study of the third-order correlation function, we show that the tunneling effect can also be enhanced by feedback. In addition, we discuss the application of feedback on Schrödinger-cat state generation in an optomechanical system. The result shows that the fidelity of cat state generation can be improved in the presence of feedback loop.

Co-N-Si/AC Catalyst for Aerobic Oxidation of Benzyl Alcohols to Esters under Mild Conditions.

A stable, earth-abundant, reusable cobalt-based heterogeneous catalyst is developed for the oxidative esterification of alcohols under ambient conditions, featuring broad substrate scope, providing good to excellent product yields. This protocol enables easy recyclability of the catalyst, measured up to five times without significant loss of efficiency. The active sites of Co-N-Si/AC are proposed to be Co-N species.

Spatial distribution, risk assessment, and source identification of heavy metals in water from the Xiangxi River, Three Gorges Reservoir Region, China.

Heavy metals (HMs) contamination in rivers has attracted wide concern due to its persistence and potential risks to the natural environment and human health. In this study, eight HMs (As, Hg, Cu, Pb, Ca, Zn, Mn, and Ni) were measured by inductively coupled plasma mass spectrometry in 24 water samples to investigate HMs contamination levels in the Xiangxi River of the Yangtze River basin. A geographic information systems kriging interpolation method was used to reveal the spatial distribution of HMs contamination. The results indicate that most HMs occurred at acceptable levels below the Surface Water Quality Standard (GB 3838-2002), with the highest concentration (23.23 mg kg-1) of Mn being observed at sampling site X20. The values of the potential ecological risk index (RI) suggest that high potential ecological risks were present at sampling sites X1, X3, X4, X14, X16, X17, and X24, which reached moderate risk level. The highest value of RI (279.56) was observed at site X17. HM spatial distributions show that upstream pollution is more severe than downstream. The hazard index was below 1 for all HMs except for Mn, indicating that HMs in Xiangxi River pose a low risk to human health. HM source identification was accomplished using principal component analysis and Pearson's correlation. Cu, Cd, Ni, and Hg originate primarily from agriculture, while Pb, Zn, and As originate primarily from transportation and mining. This research provides a reference on the risks posed by HMs in Xiangxi River and will support efforts to protect and improve water quality in Xiangxi River.

Celastrol exerts anti-inflammatory effect in liver fibrosis via activation of AMPK-SIRT3 signalling.

Celastrol, a pentacyclic tritepene extracted from Tripterygium Wilfordi plant, showing potent liver protection effects on several liver-related diseases. However, the anti-inflammatory potential of celastrol in liver fibrosis and the detailed mechanisms remain uncovered. This study was to investigate the anti-inflammatory effect of celastrol in liver fibrosis and to further reveal mechanisms of celastrol-induced anti-inflammatory effects with a focus on AMPK-SIRT3 signalling. Celastrol showed potent ameliorative effects on liver fibrosis both in activated hepatic stellate cells (HSCs) and in fibrotic liver. Celastrol remarkably suppressed inflammation in vivo and inhibited the secretion of inflammatory factors in vitro. Interestingly, celastrol increased SIRT3 promoter activity and SIRT3 expression both in fibrotic liver and in activated HSCs. Furthermore, SIRT3 silencing evidently ameliorated the anti-inflammatory potential of celastrol. Besides, we found that celastrol could increase the AMPK phosphorylation. Further investigation showed that SIRT3 siRNA decreased SIRT3 expression but had no obvious effect on phosphorylation of AMPK. In addition, inhibition of AMPK by employing compound C (an AMPK inhibitor) or AMPK1α siRNA significantly suppressed SIRT3 expression, suggesting that AMPK was an up-stream protein of SIRT3 in liver fibrosis. We further found that depletion of AMPK significantly attenuated the inhibitory effect of celastrol on inflammation. Collectively, celastrol attenuated liver fibrosis mainly through inhibition of inflammation by activating AMPK-SIRT3 signalling, which makes celastrol be a potential candidate compound in treating or protecting against liver fibrosis.

Generation of entangled Schrödinger cat state of two macroscopic mirrors.

We propose a scheme to generate the macroscopic entangled Schrödinger cat state of two mechanical resonators in a hybrid optomechanical system by introducing modulated photon-hopping interaction between two cavities. We show that the obtained entangled cat state possesses large average phonon number and the two base vectors of which are nearly orthogonal, thus causing the high degree of entanglement. To justify the robust of the scheme, the dissipation of the system and the noise from the environment are considered. It shows that the high fidelity between the obtained state and the target state can be achieved in the presence of dissipation and thermal noise within our parameter regions, which suggests that our state-generation proposal is feasible.

Hydroxamic Acid Derivatives of ß-Carboline/Hydroxycinnamic Acid Hybrids Inducing Apoptosis and Autophagy through the PI3K/Akt/mTOR Pathways.

Naturally occurring ß-carbolines are known to have antitumor activities but with limited effectiveness. In order to improve their efficacy, a series of new hydroxamic-acid-containing ß-carbolines connected via a hydroxycinnamic acid moitey (12a-f) were developed to incorporate histone deacetylase (HDAC) inhibition for possible synergistic effects. When evaluated in in vitro assays, most of the analogues showed significant antitumor activities against four human cancer cells. In particular, 12b showed the highest cytotoxic potency of the series, including drug-resistant Bel7402 cells, but had minimal effect on normal hepatic LO2 cells. These compounds also showed excellent inhibitory effects against HDAC1/6, which appear to contribute greatly to their antiproliferative properties. Compound 12b enhanced the acetylation levels of histone H3 and α-tubulin and induced greater cancer cell apoptosis than the FDA-approved HDAC inhibitor SAHA by regulating expression of apoptotic proteins Bax, Bcl-2, and caspase 3. Importantly, 12b also induced a significant amount of autophagic flux activity in Bel7402 cells by increasing the expression of Beclin-1 and LC3-II proteins and decreasing that of LC3-I and p62. Finally, 12b significantly inhibited PI3K/Akt/mTOR signaling, an important cell-growth-promoting pathway aberrantly activated in many cancers. Together, the results suggest that these hydroxamic-acid-containing ß-carboline derivatives may be new leads for the discovery of agents for the treatment of human carcinoma cancers.

Optomechanical quadrature squeezing in the non-Markovian regime.

Squeezing of quantum fluctuation plays an important role in fundamental quantum physics and has marked influence on ultrasensitive detection. We propose a scheme to generate and enhance the squeezing of mechanical mode by exposing the optomechanical system to a non-Markovian environment. It is shown that the effective parametric resonance term of mechanical mode can be induced due to interaction with the cavity and non-Markovian reservoir, thus resulting in quadrature squeezing of the mechanical resonator; jointing the two kinds of interactions can enhance the squeezing effect. Compared with the usual Markovian regime, we can obtain stronger squeezing, and, significantly, the squeezing can approach a low asymptotic stable value.

Transition-metal-catalyst-free synthesis of anthranilic acid derivatives by transfer hydrogenative coupling of 2-nitroaryl methanols with alcohols/amines.

By using a transfer hydrogenative coupling strategy, we herein describe a new method for the efficient synthesis of anthranilic acid derivatives, a significantly important class of compounds with extensive applications in organic synthesis and the discovery of bioactive molecules, from 2-nitroaryl methanols and readily available alcohols/amines. The synthesis proceeds with the merits of no need for a transition metal catalyst, operational simplicity, broad substrate scope, good functional tolerance, and high step efficiency, which offers a useful alternative to access anthranilic acid derivatives.

Straightforward synthesis of quinolines from enones and 2-aminobenzyl alcohols using an iridium-catalyzed transfer hydrogenative strategy.

A new protocol for the direct synthesis of quinolines from enones and 2-aminobenzyl alcohols via iridium-catalyzed transfer hydrogenative reactions has been demonstrated. This method employs easily available [IrCp*Cl2]2/t-BuOK as the efficient catalyst system, proceeding with the merits of high step- and atom efficiency, mild reaction conditions and operational simplicity. The experimental studies suggest that the reactions start with transfer hydrogenation, followed by the Friedländer reaction to give the final products.

Selective synthesis of nitrogen bi-heteroarenes by a hydrogen transfer-mediated direct α,ß-coupling reaction.

By an external hydrogen transfer-mediated activation mode, we herein demonstrate a new palladium-catalyzed direct α,ß-coupling of different types of N-heteroarenes. Such a selective coupling reaction proceeds with the advantages of operational simplicity, high atom-economical efficiency, and use of safe and abundant i-propanol as the activating agent, offering a practical way to access nitrogen bi-heteroarenes. Preliminary exploration has revealed that the obtained bis-1,10-phenanthroline 2qq' as a ligand is capable of improving a copper catalyst for C-C bond formation. The work reported in this paper has built an important basis for the creation of extended π-conjugated systems that are of high significance in biological, medicinal, materials and synthetic organic chemistry as well as catalysis.

Transcript and metabolite alterations increase ganoderic acid content in Ganoderma lucidum using acetic acid as an inducer.

Acetic acid at 5-8 mM increased ganoderic acid (GA) accumulation in Ganoderma lucidum. After optimization by the response surface methodology, the GA content reached 5.5/100 mg dry weight, an increase of 105% compared with the control. The intermediate metabolites of GA biosynthesis, lanosterol and squalene also increased to 47 and 15.8 µg/g dry weight, respectively, in response to acetic acid. Acetic acid significantly induced transcription levels of sqs, lano, hmgs and cyp51 in the GA biosynthesis pathway. An acetic acid-unregulated acetyl coenzyme A synthase (acs) gene was selected from ten candidate homologous acs genes. The results indicate that acetic acid alters the expression of genes related to acetic acid assimilation and increases GA biosynthesis and the metabolic levels of lanosterol, squalene and GA-a, thereby resulting in GA accumulation.

Radical alkylation and protonation induced anti-Markovnikov hydroalkylation of unactivated olefins via cobalt catalysis.

Although strategies of olefin hydroalkylation continue to emerge rapidly, the precise control of the regio- or chemoselectivity and the expansion of the reaction range are still challenges. Herein, a straightforward route for cobalt-catalyzed anti-Markovnikov hydroalkylation of unactivated olefins with alkyl iodides has been achieved. The developed reaction is compatible with oxa-, aza-, cyclo- and a series of other functional groups as well as the frameworks of some bioactive compounds. Mechanism studies confirm that an alkyl radical is involved and cobalt-alkyl insertion followed by protonation with water are possible pathways in this reaction.

Copper-Mediated Cyclization of Terminal Alkynes with CF3-Imidoyl Sulfoxonium Ylides To Construct 5-Trifluoromethylpyrroles.

A copper-mediated [3 + 2] cyclization of CF3-imidoyl sulfoxonium ylides and terminal alkynes has been demonstrated. This work provides a practical approach for assembling 5-trifluoromethylpyrroles with the merits of a broad substrate scope, good functional tolerance, and mild reaction conditions. Control experiments and DFT studies indicate that this reaction may involve the addition of π-bonds of terminal alkynes by copper-carbene radicals and hydrogen migration.